OOxxiiddaattiioonn ooff AAllccoohhooll CCoommppoonneenntt ooff MMiiccrrooeemmuullssiioonn bbyy

LLiippoopphhyylliicc CCrr((VVII))

AA DDiisssseerrttaattiioonn

SSuubbmmiitttteedd iinn Partial fulfillment

FOR THE DEGREE OF

MASTER OF SCIENCE IN CHEMISTRY

Under The Academic Autonomy

NATIONAL INSTITUTE OF TECHNOLOGY, ROURKELA

By Santosh Kumar Behera

Roll No-409cy2006

Under the guidance of

Dr. Sabita Patel

Department of Chemistry

National Institute of Technology, Rourkela

2

Dr. Sabita Patel

Asst. Professor

Department of Chemistry

National Institute of Technology

Rourkela-769008, India

CERTIFICATE

This is to certify that the dissertation entitled “OOxxiiddaattiioonn ooff AAllccoohhooll CCoommppoonneenntt ooff

MMiiccrrooeemmuullssiioonn BByy LLiippoopphhyylliicc CCrr((VVii))” being submitted by Mr. Santosh Kumar

Behera to the Department Of Chemistry, National Institute Of Technology, Rourkela-

769008, for the award of the degree of Master Of Science in Chemistry, is a record of

bonafide research carried out by him under my supervision and guidance. The

dissertation report has reached the standard fulfilling the requirements of the

regulations relating to the nature of the degree.

I further certify that to the best of my knowledge Mr. Behera bears a good moral

character.

NIT-Rourkela

Date:

Sabita Patel

3

ACKNOWLEDGEMENT

I owe this unique opportunity to place on record my deep sense of gratitude &

indebtedness to Dr. SABITA PATEL, Asst.Professor, CHEMISTRY Department, NIT,

Rourkela for his scholastic guidance, prudent suggestions & persistent endeavor throughout

the course of investigation.

I owe a deep sense of reverence to Prof. B.G.MISHRA, HOD, of chemistry, NIT,

Rourkela, for giving me the opportunity to do the project work in the institute

My sincere gratitude is to Sarita Garanayak for her overall guidance, immense help,

valuable suggestions, constructive criticism & painstaking efforts in doing the experimental

work & preparing the thesis.

I express my profound gratitude to Mr.Prakash Kumar Malik, Subhasis, and

Shailesh for their ceaseless encouragement, immense help, and hearty encouragement during

my project work.

I wish to thank all the research scholar of Organic lab, NIT for help and support during

the present study..

Lastly I express my abysmal adoration & heartfelt devotion to my beloved parents

for their countless blessings, unmatchable love, affection & incessant inspiration that has

given me strength to fight all odds & shaped my life, career till today.

In the end I must record my special appreciation to GOD who has always been a

source of my strength, inspiration & my achievements.

Name: Santosh Kumar Behera

Date: 05.05.2011

4

CONTENTS

1. Introduction and literature review

2. Experimental

3. Results and Discussion

4. Conclusion

5. References

5

1. INTRODUCTION AND LITERATURE REVIEW

The concept of microemulsion was first introduced by Hoar and Schulman in 1943.1

They prepared the first microemulsions by dispersing oil in an aqueous surfactant

solution and adding an alcohol as a co-surfactant, leading to a transparent, stable

formulation. “A microemulsion is a system of water, oil, and amphiphilic compounds

(surfactant and co-surfactant) which is a transparent, single optically isotropic, and

thermodynamically stable liquid”. Microemulsions are formed when and only when

(i) the interfacial tension at the oil/water interface is brought to a very low level and

(ii) the interfacial layer is kept highly flexible and fluid.2 These two conditions are

usually met by a careful and precise choice of the components and of their respective

proportions, and by the use of a “co-surfactant” which brings flexibility to the

oil/water interface.2

These systems are currently of interest due to its application in the following fields.3

Microemulsions in enhanced oil recovery.

Microemulsions as fuels

Microemulsions as lubricants, cutting oils and

corrosion inhibitors

Microemulsions as coatings and textile finishing

Microemulsions in detergency

Microemulsions in cosmetics

Microemulsions in agrochemicals

Microemulsions in food

6

Microemulsion in pharmaceuticals as drug delivery systems

Microemulsions in environmental remediation and

Detoxification

Microemulsions in analytical applications

Microporous media synthesis (microemulsion gel technique)

Microemulsions as liquid membranes

Microemulsions in biotechnology

Furthermore microemulsions are gentle solvents for extraction of proteins without

altering their enzymatic or functional properties although the process can readily be

scaled by conventional liquid–liquid extraction techniques. Therefore this can also be

used for bioseparations.

Due to varied consistencies and microstructures, microemulsions have been used as a

reaction media for a variety of chemical reactions such as synthesis of nanoparticles,4

polymerization,5,6,7

photochemical, electrochemical and electrocatalytic and organic

synthesis.

Zhou et al.8 have investigated the bicontinuous microemulsions made from dodecane,

water, and didodecyldimethylammonium bromide (DDAB) as media for the catalytic

reduction of trans- 1,2-dibromocyclohexane (DBCH) and for SN2 reactions of n-alkyl

bromides with electrochemically generated Co(1) complexes. Macrocyclic complexes

vitamin B 12 (a cobalt corrin) and Co(salen) resided in the water phase, while the

alkyl bromides resided in the oil phase of the microemulsion. Rates of DBCH

reduction is 40-fold larger in the bicontinuous fluid than in a water-in-oil

microemulsion which is attributed to the larger interfacial area of the bicontinuous

7

system. Formal potentials in the microemulsion depended on specific interactions,

such as those of [Col(salen)]- with cationic surfactant head groups or the influence of

water phase pH on vitamin B12.

Shrikhandea et al.9

have studied the condensation between benzaldehyde and acetone

in a cationic o/w microemulsion prepared from the combination of n-butanol as co-

surfactant, n-hexane as oil and cetyltrimethylammonium bromide (CTAB) as the

cationic surfactant (Scheme 1). They have also determined the hydrodynamic

diameters of the oil droplets in the o/w microemulsion at different compositions using

dynamic light scattering. Various parameters influencing the formation of

microemulsions, like oil content, surfactant content, oil and co-surfactant ratio were

varied and their corresponding effects on the solubilization of reactants and rate of a

condensation reaction were studied. A direct correlation between the droplet size of

the microemulsion and rate of the reaction is observed. The changes in solubility of

benzaldehyde in the microemulsion affect the reaction rate while the composition of

the oil phase does not influence the rate of the reaction.

Scheme-1

From this study they have concluded the that, the solubilization capacity of

benzaldehyde is decreased with the increase in oil + co-surfactant and the surfactant

content, indicating that the aldehyde is solubilized at the interface rather than the core

of the droplet. Further from the decrease in observed reaction rate constants on

variation in oil + co-surfactant and surfactant content further indicate that the reaction

takes place at the interface.

8

The atmospheric and electrochemical oxidation of AA(Ascorbic acid) in the SDS

micellar solutions and in the microemulsions pentanol/water stabilized by SDS have

been studied by Szymul et al.10

(Scheme-2). They found that the hydrophilic vitamin

C readily dissolves in water and O/W microemulsions as well as undergoes the

irreversible two-electron oxidation reaction and the atmospheric oxidation of AA is

accelerated by the SDS up to the CMC and inhibited in the concentrated SDS

solutions. They also found that the rate of atmospheric oxidation of ascorbic acid is

higher in the water-in-oil (W/O) than in the oil-in-water (O/W) microemulsions and

increases with the increasing oil content. The influence of the SDS on the

electrochemical behavior of vitamin C was also studied. The general conclusion

emerging from this investigation is that the increasing surfactant concentration shifts

the ascorbic acid oxidation potential to higher values whereas the corresponding peak

current values diminish. In the microemulsions the AA oxidation is slowed down by

increasing the pentanol amount in the system.

The oxidation reaction of L-ascorbic acid

Sathishkumar et al11

were synthesized n-Hexyl- -d-glucopyranoside (HGP) through

the -glucosidase-catalyzed condensation of glucose and hexanol in an aqueous-

organic bicontinuous microemulsion system with both water and oil as continuous

Scheme-2

9

phases. Methodology for separation of HGP from the microemulsion system for

analysis by gas chromatography was developed. Various factors influencing the

synthesis of HGP like reaction time, enzyme concentration and temperature were

optimized experimentally. Reverse reaction (hydrolysis) occurred was also studied.

Comparison of the rate of the reaction between synthesis and hydrolysis showed the

latter to be faster, suggesting that bicontinuous microemulsion system is more

applicable to the enzymatic hydrolysis. Degradation of enzyme in bicontinuous

microemulsion system was very negligible.

10

2. EXPERIMENTAL

Synthesis of Cetyltrimethylammonium dichromate (CTADC)

CTADC was prepared (Scheme-1) by adding aqueous solution of K2Cr2O7 (0.037mol)

in small portions to the flask containing aqueous solution of cetyltrimethylammonium

bromide (CTAB) (0.2mol) with stirring.Yellow precipitate appeared immediately. It

was filtered, washed properly till the filtrate in free from trace of dichromate and

bromide. It was dried and kept in sample bottle.

The prepared yellow solid was characterized using CHN, IR and NMR analytical data.

M.Pt. 212 oC, yield: 98%.Elemental analysis: C,58.14; H, 10.65; N, 3.54; Cr, 13.11.

C38H84O7N2Cr2 requires C, 58.16; H, 10.71; N, 3.57; Cr, 13.26. IR (cm_1): 771,

879, 933, 1467, 2850, 2921, 3028, 3471. NMR (CDCl3, 300MHz): d 0.86 (t, 6H),

1.29 (m, 48H), 1.67 (m, 4H), 1.74 (m, 4H), 3.42 (s, 18H), 3.51 (m, 4H) (Scheme-3).

N

CH3

CH3

CH3

K2Cr2O7Br-

CTAB

N

CH3

CH3

CH3

Cr2O7--

2

CTADC

(Scheme 3)

11

Oxidation of Butanol by CTADC

Different microemulsions were prepared using Surfactant(TX-100,CTAB and

SDS),Cosurfactant (n-Butanol),Oil(Chloroform),Water in Acetic acid medium. Phase

diagrams were drawn for different systems. The microemulsions are used to study the

oxidation of alcohol by CTADC at varying concentrations of oxidant, butanol,

surfactant, acid etc to unveil the reaction mechanism in this medium. The product was

found to be butanal.

The kinetics of the oxidation reaction was studied using UV-Vis spectrophotometer by

monitoring the change in absorbance of CTADC at 350 nm. Pseudo first order

condition was maintained throughout the experiment. The observed rate constant kobs

was calculated using 1st order rate expression as follows.

Where OD0 , ODt, OD and t refers to optical density of CTADC at 350 nm before the

commencement of the reaction, optical density at any time t, optical density at infinite

time or after completion of the reaction and reaction time respectively. A

representative time scan spectra is given in figure. 1.

12

Figure 1: representative UV-Vis time scan plot for the oxidation of butanol by

CTADC in microemulsion medium

0

0.1

0.2

0.3

0.4

0.5

0.6

300 350 400 450 500 550

Ab

sorb

ance

Wave length in nm

13

3. RESULTS AND DISCUSSION

Cr(VI) is known for its versatility the oxidation reaction. It can oxidise a variety of

substrates alkane, alcohol, aldehyde, thiols etc. For the oxidation process it generally

requires a high concentration of concentrated sulphuric acid. For which it is very

difficult to undertake reactions in milder conditions for acid sensitive compounds.

Further the insolubility of potassium dichromate in non-aqueous solvents makes the

oxidation process difficult and tedious for water insoluble organic substrates. To

overcome these difficulties different Cr(VI) oxidants are explored with counter ions

like ammonim, phosphonium etc.

An onium ion, as the counterion for anionic oxidants, makes a lot of difference in

oxidation potential of the oxidant as well as to the oxidizing system.12

A large number

of Cr(VI) oxidants with onium ions have been reported. 12

In a continuation of our efforts to explore some biomimetic oxidants to oxidize

organic substrates in organic solvents, we have reported the oxidation behavior of

cetyltrimethylammonium dichromate (CTADC) toward various organic substrates.

This reagent is water insoluble and stable at room temperature for more than a year

when kept in sealed bottle. It absorbs around 353-383 nm. Exists as a tight ionpair and

forms monolayer on water surface with area/molecule 51 Å2.13

Although Cr(VI) is

undisputedly carcinogenic, the insolubility in water reduces contamination of Cr(VI)

in aqueous medium, and the compound thus can be used as a green reagent. Further,

CTADC is devoid of an acidic proton and thus is relatively milder than other Cr(VI)

oxidants. In the absence of acid, CTADC exhibits some bizarre reactions with

14

nonconventional products. Aromatic amines are found to yield corresponding diazo

compounds,14

and arylaldoximes yielded corresponding nitriles.15

In an oxidation reaction of cholesterol with CTADC, Patel et al.16

have observed that

7-dehydrocholesterol is obtained instead of usual product cholestenone. This

dehydrogenation is a rare event in Cr(VI) oxidation studies, and it is explained

through remote functionalization mechanism where the cetyltrimethylammonium ion

provides a favourable environment for proper orientation of the dichromate group so

that the removal of hydrogen from 7th

and 8th

position becomes easier.

Owing to the applicability of CTADC as biomimetic oxidant, present project aims at

the oxidation of different substrates in microemulsion medium which is mimicking the

cell structure. We have chosen butanol as the substrates for the oxidation process.

Oxidation of alcohol by CTADC in nonaqueous medium has benn studied extensively

by Patel and Mishra17

. A Michaelis- Menten type kinetics was reported by them with

change in substrate concentration (Figure 2). From the dependence of rate with

various factor and order with respect to all the reactants the following rate expression

(eq 3) and mechanism has been proposed (Scheme 4).

22

1

][

11

kAlcoholKkkobs

(3)

15

(Scheme 4)

Figure 2

To study the oxidation reaction in microemulsion medium, we have constructed the

phase diagrams with varying concentration of the components (Figure 8). In all the

phase diagrams chloroform is used as oil phase because of the solubility of CTADC in

chloroform. The surfactants used are Triton X-100 (TX100) a non-ionic surfactant,

Cetyltrimethylammonium bromide (CTAB) a cationic surfactant and sodium

16

dodecylsulphate (SDS) an anionic surfactant with different composition with the

cosurfactant n-butanol. Acetic acid is used as catalyst for the oxidation process.

CTAB: nBuOH(1:6.5),Chloroform,Water CTAB: nBuOH (1:6.5), Chloroform,CTADC,Water

SDS:nBuOH(3:1),Chloroform,Water

SDS:nBuOH(3:1),Chloroform,Water

Fig-3a Fig-3b

Fig-3c Fig-3d

17

Figure 3 (a-i): represents the Pseudo-ternary phase diagram of the microemulsion

system at different S/CS ratios. E, W and O in all the plots represents 100%

emulsifier, 100% water and 100% oil respectively. The shaded regions in the diagrams

represent turbid zone and the rests are clear domain.

From these pseudoternary phase diagram it is seen that microemulsion in presence of

CTAB have less clear region than that of the anionic surfactant such as SDS. In SDS

microemulsion the clear region that is the Winsor-IV domain is larger in presence of

SDS:nBuOH(3:1),Chloroform,CTADC,AcOH,Water

TX-100:BuOH(1:4),Chloroform,Water

TX-100:nBuOH(1:4),Chloroform,CTADC,Water

TX-100:nBuOH(1:4),Chloroform,CTADC,AcOH

Fig-3f

Fig-3i Fig-3h

Fig-3g

18

CTADC.This may be due to the participation of CTADC as surfactant in the

formation of isotropic microemulsion.

The oxidation of CTADC in various microemulsion medium can be determined by

monitoring the depletion of the CTADC at 350 nm. The observed rate constants are

tabulated in Table 1.

Table 1: Change in kobs with Variation of TX-100 concentration for the oxidation

of butanol by CTADC in microemulsion.[CTADC]=5 X 10-5

[Butanol]=1.8 X 10-

1[Acetic acid]=1.45 X 10

-1Temp= 25

oC.

SL.NO. [TX-100] 103 (mol) kobs x10

4 (sec

-1)

1 6.0 6.1

2 12.12 6.5

3 18.2 6.7

4 24.26 8.1

5 30.32 9.6

From the table it is clear that with increase in surfactant concentration rate constant

increases, hence rate increases. This may be attributed to the higher solubility of

CTADC and n-butanol in micellar region which increases the amount of reactants in

close proximity which in turn increases the rate of the reaction.

19

Table 2: Change in kobs with Variation of CTADC concentration for the oxidation of

butanol by CTADC in microemulsion. [Butanol]= 1.8 X 10-1

, [Acetic acid]= 1.45 X 10-1

, Temp. = 25 oC

SL.NO. [CTADC] x 105(mol) Kobs x 10

4(sec

-1)

1 0.83 3.6

2 1.66 4.9

3 3.33 5.5

4 5.0 5.6

Figure 4: Plot of Log (rate) vs. Log[CTADC] for the oxidation of butanol in

microemulsion formed by TX 100.

20

Table 3: Change in kobs with Variation of Acetic acid concentration for the

oxidation of butanol by CTADC in microemulsion.[CTADC]= 2 X 10-5

,

[Butanol]= 1.8 X 10-1

,[Acetic acid]= 1.45 X 10-1

Temp.= 25 oC.

SL.NO. [AcOH] x 101(mol)

kobs x 10

4 (sec

-1)

1 3.5 4.0

2 6.72 7.2

3 10.11 8.4

4 12.9 12.3

5 15.88 23.4

From this data in table 4 it is seen that with increase in CTADC concentration rate of

the reaction increases. From the plot of log[rate] vs. log[CTADC] (figure 4) the order

with respect to CTADC is found to be 1. With increase in acetic acid concentration the

rate increases with an uncatalytic rate 1.1 x 10-4

.

Table 4: Change in kobs with Variation of butanol concentration for the oxidation

of butanol by CTADC in microemulsion. [CTADC]= 2.5 X 10-5

[Acetic acid]=

1.45 X 10-1

,Temp.= 25 oC

SL.NO. [Butanol] x 105 (mol) Kobs x 10

4(sec

-1)

1 3.64 9.6

2 7.28 11.5

3 10.92 23.0

4 14.57 38.38

5 18.2 22.03

6 21.85 8.1

7 25.5 6.9

8 29.13 5.8

21

Figure5: Plot of kobs versus [n-butanol] in the oxidation of butanol by CTADC in

microemulsion medium.

With increase in butanol concentration in the mixture, the rate of a reaction increases

up to the concentration of 14.57 x 10-4

of butanol then it sharply decreases (figure.5).

This may be attributed to the structural change accompanied at higher concentration of

butanol. As the n-butanol concentration increases in the micellar interface, replaces

the CTADC. CTADC gets penetrated towards the micellar core as the solubility is

higher in the non-polar medium. So the availability of CTADC in the interface region

decreases. Hence protonation of H+ with dichromate ion decreases. At higher butanol

concentration, due to the increase partition of the reactants H+, CTADC and n -

butanol in different medium the rate of the reaction decreases.This phenomenon is

shown in the following figure. 6.

22

Figure 6: Schematic representation of partition of butanol and CTADC in

microemulsion with increase in butanol content

4. Conclusion

Oxidation of butanol in microemulsion by CTADC (Lipophylic oxidation) has been

undertaken. The reaction is 1st order with respect to the oxidant CTADC. With increase in

surfactant concentration and acid concentration rate of the reaction increase.With increase in

n-Butanol concentration rate increases up to 15x10-2

M and the order with respect to butanol

is found to be1. After 15x10-2

M concentration of n-butanol rate decreases due to structural

change.

23

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1. Hoar T.P. and Schulman J. H. Nature, 152 (1943) 102..

2. Kreilgaard M. Bulletin Technique Gattefosse, 95 (2002) 79.

3. Paul Bidyut K., Moulik Satya P., Current science, 80 (2001) 8.

4. Kizling J., Boutonnet M., Stenius P., Touroude R., Maire G., in

Electrochemistry in Colloids and Dispersions ,1992, p. 33.

5. Kumar P., Mittal K. L., in Handbook of Microemulsion Science and

Technology, Marcel Dekker Inc., New York, 1999; Malmsten, M., pp. 755–

771; Guo, R. and Zhu, X., pp. 483–497; Osseo-Asare, K., pp. 549–603;

Candau, F., pp. 679–712; Bunton, C. A. and Romsted, L. S., pp. 457–482.

6. Candau F., Anquetil J., in Micelles, Microemulsions and Monolayers:

Science and Technology .1998, p. 193.

7. Gan L. M., Chew C. H., Polymeric Materials Enclyclopedia, 6 (1996) 4321.

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E.S., Yun,

S.E., Munb, S.P., Rusling, J.F., Enzyme

Micribial Tech.,42 (2008) 252.

12. Patel, S., Mishra, B. K., Tetrahedron, 63 (2007) 4367.

13. Mishra, B. K., Sahu, S., Pradhan, S., Patel, S., Indian J. Chem, 48A (2009)

1527.

14. Patel, S., Mishra, B. K., Tetrahedron Letters, 45 (2004) 1371.

15. Sahu, S., Patel, S., Mishra, B. K., Synthetic Commun., 35 (2005) 3123.

16. Patel, S., Mishra, B. K., J. Org. Chem, 71 (2006) 3522.

17. Patel, S., Mishra, B. K., J. Org. Chem, 71 (2006) 6759.